KR20200073029A - A process for producing an ultraviolet curable adhesive resin composition containing an adhesion promoting agent and an ultraviolet curable adhesive resin composition thereof - Google Patents

Abstract

The present invention relates to a method of manufacturing an ultraviolet-curable adhesive resin composition including an adhesion-promoting agent, and the ultraviolet-curable adhesive resin composition manufactured thereby, capable of improving compatibility. According to the present invention, the method of manufacturing the ultraviolet-curable adhesive resin composition includes: a) inserting at least one selected from maleinized polybutadiene and styrene-maleic acid anhydride copolymer, hydroxy ethylene acrylate (HEA), and a catalyst into a reactor, and mixing the at least one selected from the maleinized polybutadiene and the styrene-maleic acid anhydride copolymer, the HEA, and the catalyst; (b) increasing a temperature inside the reactor to 30 to 50 °C to synthesize an adhesion-promoting agent; (c) mixing the adhesion-promoting agent with an adhesion-imparting agent, a photoinitiator, a plasticizer, monomer, and oligomer to prepare the ultraviolet-curable adhesive resin composition; and (d) defoaming the prepared adhesive resin composition.

Description

A method for producing an ultraviolet curable adhesive resin composition containing an adhesion promoter and an ultraviolet curable adhesive resin composition prepared thereby {A process for producing an ultraviolet curable adhesive resin composition containing an adhesion promoting agent and an ultraviolet curable adhesive resin composition thereof}

The present invention relates to a method for manufacturing a UV-curable adhesive resin composition and a UV-curable adhesive resin composition prepared thereby, and more specifically, UV light including an oligomeric adhesive promoter having improved compatibility by having hydrophilicity and hydrophobic groups in the main chain. It relates to a method for producing a curable adhesive composition.

As the modern society rapidly develops into the information age, the importance of a high-brightness, high-resolution, large-area flat panel display with various functions in the information and video industry is increasing. 2. Description of the Related Art Development of display devices has progressed toward slimming, large-sized, and high-performance LCDs until recently, but the development of next-generation display devices such as flexible displays has emerged as a new issue in line with the rapidly changing use environment.

Commercialization of the flexible display started with a smartphone, and the initial flexible display was developed in the form of electronic paper (EPD, Electrophoreic Display), but it has been developed with shortcomings such as low color reproducibility, slow response time, and low resolution. An organic light emitting diode (OLED) is the most promising technology as an alternative to overcoming EPD in situations that have not been done. OLED is considered to be the most suitable way to make a flexible display because it can produce a module with a thin thickness because it emits light, unlike LCD that emits light through a back light unit (BLU).

In the case of OLED, problems such as pixel shrinkage, dark spots, and electrode oxidation occur when exposed to moisture and oxygen, so the encapsulation of the OLED display is understood as an important core technology to prevent this. have. The most important factor in the encapsulation process is hygroscopicity, which requires more than 10,000 times lower hygroscopicity than LCD. In addition, it is technically difficult to ensure that flexibility suitable for a flexible display is also guaranteed.

There are three encapsulation processes that are applied to OLEDs, including fine glass encapsulation, thin film encapsulation, hybrid encapsulation, and a flexible method suitable for flexible displays. These include thin film encapsulation and hybrid encapsulation. Therefore, the point/adhesive film applied to the OLED encapsulation process is required to have high adhesion and waterproof properties, and in order to secure these properties, development has been focused on materials with hydrophobicity from the material design stage.

Recently, the use of organic adhesive films is increasing due to the miniaturization and thinning of the overall display industry centering on mobile smart devices, and accordingly, the scope of application of the ultraviolet curable film having advantages such as productivity and eco-friendliness is widening.

In particular, in a composition such as an ultraviolet curable film or an ultraviolet curable adhesive, the oligomer is the most important component that determines the physical properties of the adhesive film and is the most important material for determining the hardness, adhesion, and reliability of the film. Other monomers, adhesion additives, adhesion promoters, etc. should be selected in consideration of compatibility with oligomers. Generally, commercially available adhesion promoters tend to be difficult to apply to the production of hydrophobic oligomers or monomers, mostly with hydrophilic materials. In the development of a low moisture absorption film, its application range is not wide due to compatibility problems with hydrophobic materials that are indispensably applied, and mechanical property degradation problems such as tensile strength.

Accordingly, the present invention has been studied for adhesion promoters to ensure compatibility with components such as hydrophobic oligomers and monomers, thereby completing an ultraviolet curable adhesive resin composition containing them.

1. Korea Registered Patent No. 10-13624630000 (2014.02.12) 2. Japanese Patent Publication No. 2011-107825 (2011.06.02) 3. Korean Patent Publication No. 10-2000-0061154 (2002.04.26)

The present invention aims to solve all of the above-mentioned problems.

An object of the present invention is to provide a method of manufacturing a UV curable adhesive resin composition. It is preferable to provide an ultraviolet curable adhesive resin composition containing an adhesion promoter having improved compatibility, and to improve compatibility when a hydrophobic oligomer or monomer is mixed with a hydrophilic group of the adhesion promoter.

Another object of the present invention is to provide an ultraviolet curable adhesive to improve the mechanical properties of the adhesive or adhesive film. In detail, it improves mechanical properties such as adhesive strength, curing density, tensile strength and elongation, and applies low moisture absorption and high adhesion to OLED displays that require low moisture absorption characteristics, providing applications in various fields. will be.

In order to achieve the object of the present invention as described above and to realize the characteristic effects of the present invention described later, the characteristic configuration of the present invention is as follows.

Maleinized polybutadiene and styrene-maleic anhydride copolymer according to an embodiment of the present invention, at least one selected from hydroxy ethylene acrylate (Hydroxy Ethylene Acrylate, HEA) and a catalyst are introduced into a reactor Mixing by; (b) synthesizing the adhesion promoter by raising the temperature inside the reactor to 30-50°C; (c) preparing an ultraviolet curing adhesive resin composition by mixing the adhesion promoter and the adhesion-imparting agent, the photoinitiator, the plasticizer, the monomer and the oligomer; And (d) provides a method for manufacturing a UV-curable adhesive resin composition comprising the step of degassing the prepared adhesive resin composition.

The molar ratio of the maleated polybutadiene and hydroxy ethylene acrylate in the step (a) is 1: 0.25 to 0.75.

The adhesion promoter of step (b) is a reaction of maleinized polybutadiene and hydroxy ethylene acrylate, carboxylate (Acrylates) and hydrophilic carboxylic acid (Carboxyl acid) and maleic acid as main chain polybutadiene It provides one containing an anhydride (maleic anhydride).

The catalyst may be dibutyltin dilaurate.

With respect to 100 parts by weight of the adhesive resin composition in step (c) according to an embodiment of the present invention, the adhesion promoter is 5 to 20 parts by weight, the adhesion promoter 0.5 to 15 parts by weight, the photoinitiator 1 to 5 parts by weight, the plasticizer 10 to 50 parts by weight of monomer, 20 to 50 parts by weight of the monomer and oligomer is 30 to 60 parts by weight, it provides a method for producing a UV-curable adhesive resin composition.

The adhesion agent in the step (c) includes at least one member selected from the group consisting of hydroxypropyl acrylate (HPA), hydroxybutyl acrylate (HBA) and hydroxyethyl methacrylate (2-HEMA). can do.

In the step (c), the photoinitiator may be provided with a diphenylphosphine oxide system, the plasticizer may be a hydrophobic C5 series hydrocarbon resin, and the monomer in the step (c) is at least 1 selected from monofunctional to trifunctional acrylate monomers. Species.

In the step (c) according to an embodiment of the present invention, the oligomer is mixed with (i) polybutadiene polyol, isocyanate, diluent, catalyst, and thermal stabilizer and then heated while heating the temperature to 40 to 60°C. step; (Ii) raising the temperature inside the reactor to 70 to 90° C., and then introducing a curing agent to proceed with the polyurethane reaction; (Iii) after terminating the exothermic process of the polyurethane reaction, proceeding the reaction for 1 hour to 3 hours to synthesize a prepolymer; And (iii) after the synthesis, adding hydroxyethyl acrylate (HEA) while maintaining 80 to 90° C. to introduce acrylate to the urethane end, thereby producing an ultraviolet curable adhesive resin composition. Provides a method.

The polybutadiene polyol, the oligomer is hydrogenated polybutadiene diol, the diluent is IsoNonyl Acrylate (INA), the catalyst is dibutyltin dilaurate (DBTDL), and may be a heat stabilizer (BHT).

In addition, the oligomer is characterized in that the number average molecular weight is 500 to 10,000.

Finally, an ultraviolet curable adhesive resin composition prepared according to the above manufacturing method according to an embodiment of the present invention is provided.

The adhesion promoter having improved compatibility with an oligomer according to an embodiment of the present invention is to provide a hydrophobic main chain with hydrophilic carboxylic acid (Carboxyl acid), thereby improving the compatibility when preparing a hydrophobic oligomer or monomer. .

Another object of the present invention is to provide an improvement in mechanical properties, such as an adhesive or adhesive film, including an ultraviolet curing adhesive resin composition including an adhesion promoter having improved compatibility with oligomers.

That is, it improves mechanical properties such as adhesion, cure density, tensile strength and elongation, and improves low moisture absorption and high adhesion, which are essential for OLED displays requiring low moisture absorption characteristics, thereby providing applications to various fields. will be.

Figure 1 shows the FT-IR spectra of adhesion promoters (PBCAs) according to the invention.
Figure 2 shows the results of FT-IR measurement to confirm whether the synthesis of polybutadiene-based urethane acrylate oligomer (PB-UAO) according to the present invention.
Figure 3 is prepared by manufacturing an adhesive film using a UV-curable adhesive resin composition containing an adhesion promoter according to the present invention, the contact angle (contact angle) is measured.
Figure 4 is prepared by manufacturing an adhesive film using a UV-curable adhesive resin composition containing an adhesion promoter according to the present invention, water absorption is measured.
5 is an adhesive film prepared by using an ultraviolet curing adhesive resin composition containing an adhesion promoter according to the present invention, and measures the adhesive strength (adhesion strength).
Figure 6 is a preparation of an adhesive film using an ultraviolet curing adhesive resin composition containing an adhesion promoter according to the present invention, the tensile strength (tensile strength) is measured.
FIG. 7 shows an elongation measured by preparing an adhesive film using an ultraviolet curing adhesive resin composition containing an adhesion promoter according to the present invention.

For a detailed description of the present invention, which will be described later, reference is made to the accompanying drawings that illustrate, by way of example, specific embodiments in which the invention may be practiced. These examples are described in detail enough to enable those skilled in the art to practice the present invention. It should be understood that the various embodiments of the invention are different, but need not be mutually exclusive. For example, certain shapes, structures, and characteristics described herein may be implemented in other embodiments without departing from the spirit and scope of the invention in relation to one embodiment. In addition, it should be understood that the location or placement of individual components within each disclosed embodiment can be changed without departing from the spirit and scope of the invention. Therefore, the following detailed description is not intended to be taken in a limiting sense, and the scope of the present invention, if appropriately described, is limited only by the appended claims, along with all ranges equivalent to those claimed. In the drawings, similar reference numerals refer to the same or similar functions across various aspects.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings in order to enable those skilled in the art to easily implement the present invention.

The synthesized adhesion promoter according to an embodiment of the present invention introduces an acrylate reactor and a carboxylic acid through a ring opening reaction of maleic anhydride. Furthermore, the addition amount of the adhesion promoter is specified, and an ultraviolet curable adhesive composition prepared by including the same is provided.

Maleinized polybutadiene and styrene-maleic anhydride copolymer according to an embodiment of the present invention, at least one selected from hydroxy ethylene acrylate (Hydroxy Ethylene Acrylate, HEA) and a catalyst are introduced into a reactor Mixing by; (b) synthesizing the adhesion promoter by raising the temperature inside the reactor to 30-50°C; (c) preparing an ultraviolet curing adhesive resin composition by mixing the adhesion promoter and the adhesion-imparting agent, the photoinitiator, the plasticizer, the monomer and the oligomer; And (d) degassing the prepared adhesive resin composition.

Maleated polybutadiene according to an embodiment of the present invention means that maleic anhydride is grafted on a hydrophobic polybutadiene backbone (Ricon131MA10, Total Cray Valley). However, the main chain may be SMA, a styrene-maleic anhydride copolymer. Styrene Maleic anhydride copolymer is also grafted with maleic anhydride in the main chain, so it can be used as the main chain.

The maleated polybutadiene may have the following structure of [Formula 1], but is not limited thereto.

[Formula 1]

The structure of the styrene-maleic anhydride copolymer may have the structure of [Formula 2] below, but is not limited thereto.

[Formula 2]

Through the ring-opening reaction of maleic anhydride, a carboxylic acid and acrylate reactor can be introduced.

To this end, hydroxy ethyl acrylate, preferably 2-hydroxyethyl acrylate (HEA, Aldrich) can be used without purification. The 2-hydroxy ethyl acrylate is as follows [Formula 3].

[Formula 3]

Mechanism 1 for introducing a carboxylic acid and acrylate reactor through the ring-opening reaction of maleic anhydride is as follows.

[Mechanism 1]

In this case, dibutyltin dilaurate (DBTDL) may be used as the catalyst. DBTDL stands for Dibutyltin dilaurate, and is generally one of acid catalysts, base catalysts, metal complexes and amines used in esterification reactions. It is preferable that the amount of the catalyst includes 0.1 to 5 parts by weight. If it is less than the 0.1 range, there is a fear that the present reaction may not proceed properly, and if it is more than the 0.5 range, it does not affect the synthetic reaction and is meaningless.

In the present invention, maleic anhydride and hydroxy ethyl acrylate (HEA) present in a malenized polybutadiene are reacted to simultaneously introduce carboxylic acid and acrylate groups. It is provided that it is used as an adhesion promoter.

Therefore, the adhesion promoter is a reaction of maleated polybutadiene and hydroxy ethylene acrylate, and the main chain polybutadiene is acrylate and hydrophilic Carboxyl acid and maleic anhydride. It is characterized by including.

The hydrophobic polybutadiene backbone and the hydrophilic carboxylic acid are present at the same time, so compatibility with various hydrophilic and hydrophobic materials is excellent. In particular, it provides an adhesion promoter (PBCA, Poly Butadiene Carboxylic Acid) with improved compatibility with oligomers. Therefore, a UV-curable adhesive resin composition prepared by including an adhesion promoter can be produced, and when an adhesive containing the same is used, there is no deterioration in mechanical properties, and wettability with the surface of the adherend can also be secured.

The adhesion enhancer improves the wettability between the surface of the adherend (SUS 304) and the adhesive film due to the hydrophilic effect of carboxylic acid, and also has one acrylate reactor per molecule, thereby reducing the curing density. Since the flexibility of the adhesive film is improved and the internal stress is easily dispersed, it is possible to provide an effect of improving the adhesive force.

The synthesis of the adhesion promoter (PBCA) can be confirmed by FT-IR measurement, and the results are shown in FIG. 1. As the ring-opening reaction of maleic anhydride in FIG. 1 progresses, the size of the cyclic anhydride C=O absorption peaks shown in 1783cm-1 and 1862cm-1 decreases in proportion to the conversion rate, and at the same time, 1730cm-1 and 1708 Synthesis of the adhesion promoter PBCA can be confirmed by confirming that the size of the CO-1 (R=HEMA) or COOH absorption peak of cm-1 increases.

As the content of Carboxylic acid introduced into the molecule of the adhesion promoter increases, the adhesion of the adhesion film tends to increase, and mechanical properties such as surface properties, adhesion properties, and moisture absorption properties, etc., are higher than those of conventional commercial adhesion promoters. Provide improvement. This can be confirmed that the compatibility with various hydrophilic and hydrophobic materials is greatly improved due to the simultaneous presence of the hydrophobic polybutadiene backbone and hydrophilic maleic anhydride and carboxylic acid in the molecule.

The molar ratio of maleated polybutadiene and hydroxy ethylene acrylate according to an embodiment of the present invention is characterized in that it is 1: 0.25 to 0.75. In the case of the above range, after the ring-opening reaction of maleic anhydride, the ratio of introduced carboxylic acid and acrylates is optimized to maximize compatibility with oligomers and monomers. When the weight part of maleic anhydride exceeds 0.75, this is an effect of increasing the curing density by the acrylate reactor, which is present at the same content, than the effect of improving the wettability due to the increase in the content of carboxylic acid, so it is not easy to disperse the internal stress of the adhesive film. Will occur. Conversely, when it is less than 0.25, the conversion rate to hydrophilic carboxylic acid is low, so that the wetting effect decreases.

After all, the tensile strength and elongation are mainly determined by the content of the acrylate reactor present in the adhesion promoter (PBCA). As the conversion rate of maleic anhydride increases, that is, as the number of acrylate reactors increases, the tensile strength of the adhesive film increases and the elongation increases. This ratio is preferred in view of the tendency to decrease.

The number average molecular weight (Mn) of the adhesion promoter is provided from about 3,000 to 100,000, and preferably between 3,000 and 15,000 considering the reactivity and compatibility of the adhesion promoter.

In the step (c) according to an embodiment of the present invention, with respect to 100 parts by weight of the UV-curable adhesive resin composition, the adhesion promoter is 20 to 50 parts by weight, the adhesion promoter 0.5 to 15 parts by weight, the photoinitiator 1 to 5 parts by weight, The plasticizer is characterized in that 10 to 50 parts by weight, 20 to 50 parts by weight of the monomer and 30 to 60 parts by weight of the oligomer.

The adhesion promoter is preferably 5 to 20 parts by weight, and more preferably 5 to 15 parts by weight, with respect to 100 parts by weight of the ultraviolet curing adhesive resin composition.

In the above range, when maleic anhydride and HEA present in a malenized polybutadiene or a styrene-maleic anhydride copolymer are reacted with HEA to simultaneously introduce a carboxylic acid and acrylate reactor, carboxylic acid is introduced. As the content of acid increases, the adhesion of the adhesive film increases, and at the same time, the acrylate reactor combined at the same ratio as the carboxylic acid can be provided to optimize mechanical properties such as tensile strength and elongation by maintaining the curing density of the adhesive film. have.

The adhesive agent according to the embodiment of the present invention is preferably 0.5 to 15 parts by weight based on 100 parts by weight of the total resin composition, hydroxypropyl acrylate (HPA), hydroxybutyl acrylate (HBA) and hydroxyethyl methacryl It characterized in that it comprises at least one selected from the group consisting of rate (2-HEMA).

The adhesion-imparting agent may be used having a number average molecular weight of 200 to 10000, preferably a number average molecular weight of 200-3000, more preferably 300-1000. The adhesion-imparting agent may be administered to the reaction to impart or enhance adhesion performance.

The photoinitiator according to the embodiment of the present invention is characterized in that 1 to 5 parts by weight based on 100 parts by weight of the entire UV curable adhesive resin composition, preferably Darocure TPO (Ciba specialty chemical) is provided.

The monomer according to an embodiment of the present invention is provided with 20 to 50 parts by weight based on 100 parts by weight of the entire UV-curable adhesive resin composition, and may include at least one selected from monofunctional to trifunctional acrylate monomers.

Trimethylolpropane triacrylate (TMPTA, Aldrich) may be provided as the trifunctional acrylate monomer according to an embodiment of the present invention, and has a structure of the following [Formula 4].

[Formula 4]

In the case of a monomer, it is necessary to select a monomer having a hydrocarbon chain as long as possible in consideration of properties such as compatibility with hydrophobic oligomers, low toxicity, and low volatility.

Among the monomers according to the embodiment of the present invention, a monofunctional acrylate is provided, preferably a monomer of TCI commercially available as IsoNonyl Acrylate (INA) is provided and has the structure of the following [Formula 5].

[Formula 5]

The plasticizer according to an embodiment of the present invention is provided with 10 to 50 parts by weight based on 100 parts by weight of the entire UV-curable adhesive resin composition, Wingtack 86 (Total Cray Valley), which is a hydrophobic C5 series hydrocarbon resin, is provided. Corresponds to aromatically modified C5 hydrocarbon resin. However, it is not limited thereto.

The oligomer according to the embodiment of the present invention may include 30 to 60 parts by weight based on 100 parts by weight of the entire UV-curable adhesive resin composition. Oligomer means a polybutadiene-based urethane acrylate oligomer (PB-UAO).

In addition, (i) adding polybutadiene polyol, isocyanate, diluent, catalyst, and thermal stabilizer to the reactor and then mixing while heating the temperature to 40 to 60°C; (Ii) raising the temperature inside the reactor to 70 to 90° C., and then introducing a curing agent to proceed with the polyurethane reaction; (Iii) after terminating the exothermic process of the polyurethane reaction, performing a reaction for 1 hour to 3 hours to synthesize a prepolymer; And (iii) after the synthesis, adding hydroxyethyl acrylate (HEA) while maintaining 80 to 90° C. to introduce acrylate to the urethane end.

When the polyol compound and the diisocyanate compound react urethane, a substituent is inserted in the end capping method at the end of the urethane compound to include a hydroxyl group (-OH) at one end of the molecular structure. Since one hydroxy group is included at the end of the molecular structure, the adhesion to the substrate is further improved in forming a film by applying to the substrate, and further, the adhesive force is improved upon adhesion to the adherend. In addition, the mechanism of reaction proceeds as follows [Mechanism 2].

[Mechanism 2]

In the case of the oligomer, it is the most important component that determines the physical properties of the adhesive film. It is the most important material for determining the hardness, adhesion, and reliability of the film. In addition, the number average molecular weight of the synthesized oligomer (Mn) has a range of 40,00 to 50,00 g/mol, and preferably has a value near 42,200 g/mol. In addition, the viscosity measured at 60oC is 50,000 to 60,000, and preferably has a value around 50,770 g/mol.

FT-IR was measured to confirm the synthesis of the synthesized polybutadiene-based urethane acrylate oligomer (PB-UAO), and the results are shown in FIG. 2. Figure 2 (a) is a spectrum of the state before the reaction and Figure 2 (b) is a spectrum measuring the oligomer in the urethane reaction is completed, confirming that the -NCO peak near 2270 cm-1 disappeared, the urethane reaction proceeded. You can check.

The polybutadiene polyol is a hydrogenated polybutadiene diol (HLBH-P2000, Total Cray Valley), preferably Hydroxyl-Terminated Hydrogenated Polybutadiene, and in this case, the number average molecular weight is preferably about 2,000 (Mn). A commercially available HLBH-P2000 (Total Cray Valley) may be applied. The structural formula has the structure of the following [Chemical Formula 6].

[Formula 6]

The diluent is INA (IsoNonyl Acrylate), and the number average molecular weight is preferably about 200 (Mn), and a commercially available diluent from TCI may be applied. The structure of INA is as follows.

[Formula 7]

The catalyst is dibutyltin dilaurate (DBTDL), the number average molecular weight is about 600 (Mn), and commercially available Aldrich DBTDL can be used. The structural formula is as follows.

[Formula 8]

BHT, a heat stabilizer, means butylated hydroxytoluene. The number average molecular weight of BHT may be about 220 (Mn). Commercially available Aldrich BHT can be used. The structure is as shown in [Formula 9].

[Formula 9]

The isocyanate compound is toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate or naphthalene diisocyanate, 2,4-toliendiisocyanate, 2,6-toliendiisocyanate, 1,3-xyl Rendiisocyanate, 1,4-xylenediisocyanate, 1,5-naphthalenediisocyanate, 2,4-trienediisocyanate, 2,6-trienediisocyanate, 1,3-xylenediisocyanate, diphenylmethane-4,4 -Diisocyanate, 3-methyl-diphenylmethane diisocyanate, methylene diphenyl diisocyanate (MDI), 1,6-hexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 1, It may be configured to include at least one selected from the group consisting of 3-bis (isocyanatomethyl) cyclohexane and 1,4-bis (isocyanate methyl) cyclohexane. Preferably, it is Isophorone Diisocuanate (IPDI), and the number average molecular weight (Mn) is about 220. Commercially available Aldrich's can be used. In addition, the structure of IPDI is as follows.

[Formula 10]

In addition, if necessary, it may be configured by further adding a curing agent. Isocyanate has the characteristics of hydrophobicity and waterproofness, and is preferable in further including waterproofing performance in a polyurethane resin composition having impact resistance because it imparts an effect of improving the waterproofing performance and lowering the moisture content of the UV-curable adhesive resin composition including the same. It can be said to be a compound.

The curing agent may provide two or more functional groups such as an isocyanate-based, amine-based, aziridine-based, or polyisocyanate-based curing agent. Examples of the isocyanate-based curing agent include methylene diphenyl diisocyanate, hexamethylene diisocyanate, and 4,4-dicyclohexyl. Methane diisocyanate, toluene diisocyanate, and the like. Examples of polyisocyanate systems include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-diisocyanatodiphenylmethane, and xylene diisocyanate. , A polyisocyanate compound composed of a trimer such as isophorone diisocyanate or the polyisocyanate compound and ethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, polyoxyethylene glycol, long chain higher alcohol, and the like. And compounds having a plurality of isocyanate group terminals in a molecule formed by reaction of a low-molecular-active hydrogen compound or the like. In addition, when adding a curing agent to the isocyanate, if the curing agent is excessively charged, it may be hardened at an unintended time or harder than the target.

The oligomer according to an embodiment of the present invention is characterized in that the number average molecular weight is 500 to 10,000 (Mn).

An ultraviolet curable adhesive resin composition prepared according to any one of the embodiments of the present invention is provided.

In addition, the UV-curable adhesive resin composition according to an embodiment of the present invention may further include an acrylate-based adhesive composition for enhancing adhesion. In general, the acrylate-based adhesive composition applied to the adhesive may include all, specifically, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentadinyl (meth)acrylate and combinations thereof, acrylic acid Rubbers such as alkyl ester-based resins, styrene-butadiene copolymers, polyisoprene rubbers, and polybutylene rubbers, polyvinyl ether-based, silicone-based, maleimide-based, cyanoacrylate-based resins, vinylidene chloride, and vinylidene fluoride, etc. And a fluorine-based (meth)acrylic resin containing a vinylidene halide resin and a fluorine-containing alkyl acrylate polymer component, but is not limited thereto.

The organic solvent for constituting the UV-curable adhesive resin composition according to the embodiment of the present invention may include all of the organic solvents that can be used to constitute the general adhesive composition, and more specifically acetone, methanol, ethanol, methyl ethyl ketone, And toluene, ethyl acetate, butyl acetate, acetone, butyl carbitol, butyl carbitol acetate, butyl cellosolve, butyl cellosolve acetate, and terpineol. It is preferable that the solvent is contained in less than 30 parts by weight based on 100 parts by weight of the total composition, and when more than 30 parts by weight of a solvent is included, viscosity becomes low, and there is a fear that the solvent may flow when applied to the substrate to form an adhesive, while the solvent volatilizes. Bubbles may be formed on the surface. In addition, when applied to less than 30 parts by weight, the impact resistance of the touch panel can be improved, and since the printing step difference on the surface can be absorbed, it has excellent properties as an adhesive. Therefore, it is important to add an excessive amount of solvent. Since the organic solvent is a compound added to control the concentration during the polymerization reaction, it may be included at any stage of the compound preparation step.

Otherwise, according to the present invention, additives are leveling agents, antifoaming agents, stabilizers, antioxidants, surfactants, and ultraviolet absorbers. It may include at least one or more selected from wetting agents and rust inhibitors.

At this time, the stabilizer is a specific example of diethyl ethanolamine, a third amine such as trihexylamine, hindered amine, organic phosphate, hindered phenol, gelatin, methylcellulose, hydroxy ethyl cellulose, hydroxypropyl cellulose , Water-soluble polymers such as carboxymethyl cellulose, polyethylene glycol, polyoxyethylene-polyoxypropylene block copolymer, polyacrylamide, polyacrylic acid, polyacrylic acid salt, sodium alginate, polyvinyl alcohol partial saponification, tricalcium phosphate, titanium oxide , Calcium carbonate, silicon dioxide, but is not limited thereto. In addition, the surfactant that may be added for dispersion stabilization may include any one or more of sodium dodecylbenzenesulfonate, sodium dialkylsulfosuccinate, sodium lauryl sulfate, or polyethylene glycol nonylphenyl ether, as a specific example, but is not limited thereto. It does not work.

Example

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is provided as a preferred example of the present invention and cannot be interpreted as limiting the present invention by any means.

The contents not described herein will be sufficiently technically inferred by those skilled in the art, and thus the description thereof will be omitted.

Example 1-1 Preparation of adhesion promoter (PBCA)

Malenized polybutadiene (Ricon131MA10), 2-hydroxyethyl acrylate (HEA) and reaction catalyst DBTL were added to a 4-necked flask, and the mixture was uniformly mixed for 30 minutes while heating the temperature to 40 ^° C. Thereafter, the temperature inside the reactor was raised to 80 ^° C, and the reaction proceeded for 8 hours from the time the temperature was stabilized to synthesize the adhesion promoter (PBCA) in which the carboxylic acid and acrylate reactors were introduced. In this case, the molar ratio of malenized polybutadiene and 2-hydroxyethyl acrylate is 1: 0.25 ((MA/HEA) = 1:0.25).

Example 1-2 Preparation of adhesion promoter (PBCA)

The molar ratio of malenized polybutadiene and 2-hydroxyethyl acrylate was prepared in the same manner as in Example 1-1 except for the point of 1:0.50.

Example 1-3 Preparation of adhesion promoter (PBCA)

The molar ratio of malenized polybutadiene and 2-hydroxyethyl acrylate was prepared in the same manner as in Example 1-1, except that the point was 1: 0.75.

Example 1-4 Preparation of adhesion promoter (PBCA)

The molar ratio of malenized polybutadiene and 2-hydroxyethyl acrylate was prepared in the same manner as in Example 1-1 except for the 1:1 point.

Examples 1-1 to 1-4 are shown in [Table 1].

Example 1-1 Example 1-2 Example 1-3 Example 1-4 Ricon131MA10
(Mw=5,000,
MA per chain=5) g 97.17 94.5 91.98 89.59 mol 0.019 0.019 0.018 0.018 MA mol 0.097 0.095 0.092 0.090 HEA
(Mw=116.12) g 2.82 5.49 8.01 10.4 OH mol 0.024 0.047 0.069 0.090 Mole Ratio (MA/HEA) 1 / 0.25 1 / 0.5 1 / 0.75 1/1

Comparative Example 1-1 Preparation of adhesion promoter (PBCA)

Malenized polybutadiene (Ricon131MA10), 2-hydroxyethyl acrylate (HEA) and reaction catalyst DBTL were added to a 4-neck flask, and the mixture was uniformly mixed for 30 minutes while heating the temperature to 40 ^° C. Thereafter, the temperature inside the reactor was raised to 80 ^° C, and the reaction proceeded for 8 hours from the time the temperature was stabilized to synthesize the adhesion promoter (PBCA) in which the carboxylic acid and acrylate reactors were introduced.

For the comparative evaluation, the adhesion promoter of the conventional commercially available adhesion enhancer TCI's Mono-2-(methacryloyloxy)ethyl succinate (HEMA succinate) was used.

Example 2 Polybutadiene-based urethane acrylate oligomer (PB-UAO)

To prepare an ultraviolet curable adhesive film for evaluation of the adhesion promoters prepared in Examples 1-1 to 4, a urethane acrylate oligomer having a hydrophobic polybutadiene backbone was synthesized. Polyol (HLBH-P2000 Diol Monomer), isocyanate and reactive diluent INA, and catalyst (DBTDL) and heat stabilizer (BHT) were added to the 4-neck flask, and the temperature was increased to 60°C. The mixture was uniformly heated for 1 hour while heating. Thereafter, the temperature inside the reactor was raised to 85° C., and the urethane reaction was performed while slowly dropping IPDI for 20 minutes when the temperature stabilized. While confirming the temperature change due to heat generation during the urethane reaction, the reaction was continued for 2 hours after the heating was stopped to synthesize a urethane prepolymer in which an isocyanate reactor was attached to the terminal. Thereafter, the acrylate reactor was introduced at the end of the synthesized urethane prepolymer by adding HEA while maintaining the reactor temperature at 85°C. A hydrophobic PB-UAO composed of a polybutadiene main chain was synthesized after confirming that the characteristic peak of the -NCO group completely disappeared through FT-IR measurement in the middle of the reaction.

Example 3-1

Preparation of adhesive film using UV curable adhesive resin composition containing 5 parts by weight of adhesion promoter

PB-UAO oligomer prepared in Example 2 (40 parts by weight), plasticizer (Wingtack 86, 25 parts by weight), polyfunctional acrylate monomer (TMPTA, 3 parts by weight), monofunctional acrylate monomer (INA, 30 parts by weight ) And a photoinitiator (Darocure TPO, 2 parts by weight) were uniformly mixed to prepare a reference UV-curable adhesive resin composition.

Adhesion promoter (PBCA-25%CA) of Example 1-1 of the prepared adhesive resin composition was defoamed to prepare a UV curable adhesive resin composition containing an adhesion promoter, and in the manufacturing process, an adhesion promoter and a reference UV curable adhesive resin Compatibility with oligomers or monomers in the composition was confirmed. Among the manufactured adhesive resin compositions, the adhesive resin composition, which ensures compatibility, is coated on a PET film with a thickness of 25 μm using a BAKER type film applicator to a thickness of 100 μm, and cured with a light amount of 4000 mJ using a metal halide UV lamp. A film was prepared.

Example 3-2

Preparation of adhesive film using UV curable adhesive resin composition containing 5 parts by weight of adhesion promoter

It was prepared in the same manner as in 3-1, except that it included the adhesion promoter of Example 1-2 (PBCA-50%CA).

Example 3-3

Preparation of adhesive film using UV curable adhesive resin composition containing 5 parts by weight of adhesion promoter

It was prepared in the same manner as in 3-1, except that it included the adhesion promoter of Example 1-3 (PBCA-75%CA).

Example 3-4

Preparation of adhesive film using UV curable adhesive resin composition containing 5 parts by weight of adhesion promoter

It was prepared in the same manner as in 3-1, except that it contains the adhesion promoter of Example 1-4 (PBCA-100%CA).

Comparative Example 3-1

Preparation of adhesive film using UV curable adhesive resin composition containing 5 parts by weight of adhesion promoter

For comparative evaluation, the adhesion promoter was prepared in the same manner as in Example 3-1, except that the existing commercially available adhesion promoter Mono-2-(methacryloyloxy)ethyl succinate (HEMA succinate, TCI) was used.

Example 4-1

Preparation of adhesive film using UV curable adhesive resin composition containing 10 parts by weight of adhesion promoter

It was prepared in the same manner as in 3-1, except that the adhesion promoter 10 parts by weight.

Example 4-2

Preparation of adhesive film using UV curable adhesive resin composition containing 10 parts by weight of adhesion promoter

It was prepared in the same manner as 3-2, except that the adhesive enhancer contains 10 parts by weight.

Example 4-3

Preparation of adhesive film using UV curable adhesive resin composition containing 10 parts by weight of adhesion promoter

It was prepared in the same manner as 3-3, except that the adhesion promoter 10 parts by weight.

Example 4-4

Preparation of adhesive film using UV curable adhesive resin composition containing 10 parts by weight of adhesion promoter

It was prepared in the same manner as 3-4, except that it contains 10 parts by weight of the adhesion promoter.

Comparative Example 4-1

Preparation of adhesive film using UV curable adhesive resin composition containing 10 parts by weight of adhesion promoter

For comparative evaluation, the adhesion promoter was prepared in the same manner as in Example 4-1 except that the existing commercially available adhesion promoter Mono-2-(methacryloyloxy)ethyl succinate (HEMA succinate, TCI) was used.

Example 5-1

Preparation of adhesive film using UV-curable adhesive resin composition containing 15 parts by weight of adhesion promoter

It was prepared in the same manner as in 3-1, except that it contains 15 parts by weight of an adhesion promoter.

Example 5-2

Preparation of adhesive film using UV-curable adhesive resin composition containing 15 parts by weight of adhesion promoter

It was prepared in the same manner as 3-2, except that the adhesive enhancer contains 15 parts by weight.

Example 5-3

Preparation of adhesive film using UV-curable adhesive resin composition containing 15 parts by weight of adhesion promoter

It was prepared in the same manner as 3-3, except that it contains 15 parts by weight of an adhesion promoter.

Example 5-4

Preparation of adhesive film using UV-curable adhesive resin composition containing 15 parts by weight of adhesion promoter

It was prepared in the same manner as 3-4, except that it contains 15 parts by weight of an adhesion promoter.

Comparative Example 5-1

Preparation of adhesive film using UV-curable adhesive resin composition containing 15 parts by weight of adhesion promoter

For comparative evaluation, the adhesion promoter was prepared in the same manner as in Example 5-1, except that the existing commercially available adhesion promoter Mono-2-(methacryloyloxy)ethyl succinate (HEMA succinate, TCI) was used.

Example 6-1

Preparation of adhesive film using UV curable adhesive resin composition containing 20 parts by weight of adhesion promoter

It was prepared in the same manner as in 3-1, except that it contains 20 parts by weight of an adhesion promoter.

Example 6-2

Preparation of adhesive film using UV curable adhesive resin composition containing 20 parts by weight of adhesion promoter

It was prepared in the same manner as 3-2, except that the adhesive enhancer contains 20 parts by weight.

Example 6-3

Preparation of adhesive film using UV curable adhesive resin composition containing 20 parts by weight of adhesion promoter

It was prepared in the same manner as 3-2, except that the adhesive enhancer contains 20 parts by weight.

Example 6-4

Preparation of adhesive film using UV curable adhesive resin composition containing 20 parts by weight of adhesion promoter

It was prepared in the same manner as 3-4, except that the adhesion promoter 20 parts by weight.

Comparative Example 6-1

Preparation of adhesive film using UV curable adhesive resin composition containing 20 parts by weight of adhesion promoter

For comparative evaluation, the adhesion promoter was prepared in the same manner as in Example 6-1, except that the existing commercially available adhesion promoter Mono-2-(methacryloyloxy)ethyl succinate (HEMA succinate, TCI) was used.

One. Compatibility measurement

Examples 3-1 to 4, 4-1 to 4, 5-1 to 4 and 6-1 to 4 and corresponding Comparative Examples 3 to 6-1 were prepared, and the results of compatibility testing were shown in [Table 2]. ].

Adhesion Promoter Commercial Synthesized HEMA
Succinate
(Comparative example)
Mole Ratio (MA/HEA)
1 / 0.25 Mole Ratio (MA/HEA)
1 / 0.5 Mole Ratio (MA/HEA)
1 / 0.75 Mole Ratio (MA/HEA)
1/1 Adhesion promoter
(Parts by weight) 5 ○
Comparative Example 3-1 ○
Example 3-1 ○
Example 3-2 ○
Example 3-3 △
Example 3-4 10 △
Comparative Example 4-1 ○
Example 4-1 ○
Example 4-2 ○
Example 4-3 △
Example 4-4 15 X Comparative Example 5-1 ○
Example 5-1 ○
Example 5-2 ○
Example 5-3 X
Example 5-5 20 X
Comparative Example 6-1 X
Example 6-1 X
Example 6-2 X
Example 6-3 X
Example 6-4

2. Contact angle measurement

Phoenix 300 Touch (SEO) equipment according to Table 2 by preparing an excellent commercial example (Examples 3-1 to 3, Examples 4-1 to 3, Examples 5-1 to 3) and comparative examples corresponding thereto Was used to measure the contact angle. In addition, the contact angle was measured using distilled water. (ASTM D5946). The results are shown in FIG. 3.

3. Moisture absorption rate measurement

Prepared according to Table 2, excellent Examples (Examples 3-1 to 3, Examples 4-1 to 3, Examples 5-1 to 3) and corresponding comparative examples, 100 ^o C, 48 hours The moisture absorption rate was measured by standing in boiling water for 2 hours. The results are shown in FIG. 4.

4. Adhesion measurement

Prepared in accordance with Table 2, excellent Examples (Examples 3-1 to 3, Examples 4-1 to 3, Examples 5-1 to 3) and corresponding comparative examples, according to ASTM D-3330 standards. Accordingly, the test piece was attached to the SUS with a size of 2.5 Cm width, and the force measured when forcibly peeled at 90 degrees using a UTM device was measured, and the adhesive force was shown in FIG. 5. The unit of force is force/width (Kgf/in).

In addition, by measuring the mechanical properties such as tensile strength and elongation, the results are shown in FIGS. 6 and 7, respectively.

First, looking at the results of compatibility, the results of Examples 3 to 5 to 1 to 3 corresponding to the technical features of the present invention show excellent results in compatibility.

FT-IR measurement of the result of the contact angle shows that the amount of carboxylic acid produced increases as the amount of hydroxy ethyl acrylate (HEA) bound to the maleic anhydride increases. The result was confirmed from FIG. 1. In addition, according to Figure 3, the adhesive film containing the same amount of the adhesion promoter has a high conversion rate of maleic anhydride, that is, the contact angle of the film containing the adhesion promoter having a large amount of carboxylic acid, compared to the film containing the adhesion promoter with a low conversion rate. It showed a tendency to decrease, and in the case of an adhesion promoter having the same conversion rate of maleic anhydride, it was confirmed that the contact angle of the adhesive film decreased as its content increased. From these results, the synthesized adhesion promoter was confirmed to increase the hydrophilicity of the adhesive film surface, but it can be confirmed that the hydrophobicity of the hydrophobic polybutadiene chain maintains a relatively high hydrophobicity compared to the hydrophilic adhesion promoter HEMA succinate.

In the case of the moisture absorption rate, when HEMA succinate with strong hydrophilicity was used as the adhesion promoter, it was confirmed that the moisture absorption rate increased by about 1.5 times compared to the adhesive film without the adhesion promoter even at a content of 5 parts by weight. In the case of the synthesized adhesion promoter, a small amount of moisture absorption tended to increase compared to the adhesive film not containing the adhesion promoter due to the effect of the introduced carboxylic acid, but it was significantly lower than the HEMA succinate. This synthesized PBCA also contains a hydrophilic carboxylic acid group, such as HEMA succinate, but is composed of polybutadiene with a hydrophobic backbone, and the introduced multiple acrylate reactors increase the cure density compared with monofunctional HEMA succinate. It is judged to show a low moisture absorption rate.

Lastly, in the case of an adhesive film containing 5 parts by weight of an adhesion promoter having mechanical properties, the tensile strength and elongation tended to be lower than when the HEMA succinate was used as the adhesion promoter (PBCA). It was found to be the best in terms of adhesion. This is because HEMA succinate improves the wettability due to the effect of carboxylic acid, and monofunctional HEMA succinate improves the flexibility of the adhesive film by lowering the curing density of the adhesive film compared to the polyfunctional PBCA, so internal stress is effectively dispersed. do. In the case of the synthesized adhesion promoter (PBCA), the maleic anhydride conversion rate, that is, the higher the content of carboxylic acid, the higher the adhesion due to the improved wettability. The adhesion promoter having the same conversion rate of maleic anhydride showed an increase in the content of carboxylic acid when the content of the adhesion promoter added to the adhesive film increased, so that the adhesive force of the adhesive film increased. However, in the case of an adhesion promoter having a maleic anhydride conversion rate of 75% ((MA/HEA) = 1:0.75), the adhesive strength of the adhesive film containing 15 parts by weight is lower than that of the adhesive film containing 10 parts by weight, which is carboxylic acid Due to the effect of increasing the curing density by the acrylate reactor, which is present at the same content as the effect of improving the wettability due to the increase in the content, it is considered that the internal stress dispersion of the adhesive film is not easy and the adhesive strength is deteriorated. (MA/HEA) = 1:0.75 is 15 parts by weight of the adhesive film high cure density can be confirmed in the tensile strength and elongation measurement results of the adhesive film, as can be seen in Figures 5 and 6 (MA/HEA) = 1: It can be seen that the tensile strength and elongation change rapidly as 0.75 is increased from 10 parts by weight to 15 parts by weight. Tensile strength and elongation are mainly determined by the content of the acrylate reactor present in the adhesion promoter (PBCA). As the conversion rate of maleic anhydride increases, that is, as the number of acrylate reactors increases, the tensile strength of the adhesive film increases and the elongation decreases. Tended to.

The adhesion promoter, such as the comparative example of the currently commercialized HEMA succinate, improves the wettability between the surface of the adherend (SUS 304) and the adhesive film due to the effect of the hydrophilic carboxylic acid, and also has one acrylate reactor per molecule to lower the curing density. Since it plays a role, the flexibility of the adhesive film is improved, and the internal stress is easily dispersed, thus showing the effect of improving the adhesive force. However, the range of utilization is not wide due to the compatibility problem with hydrophobic materials, which is essential in the development of low moisture absorption films, and the mechanical property degradation problems such as tensile strength.

Therefore, in the present invention, the maleic anhydride and HEA present in the malenized polybutadiene were reacted to simultaneously introduce carboxylic acid and acrylate reactors to ensure wettability with the adherend surface without deteriorating mechanical properties, and also hydrophobic polybutadiene backbone and hydrophilic carboxylic acid The presence of acid simultaneously provides an adhesion promoter (PBCA) with improved compatibility with various hydrophilic and hydrophobic materials.

As a result of applying the synthesized adhesion promoter (PBCA) to the production of an adhesive film composed of a hydrophobic material, it was confirmed that compatibility was improved compared to the hydrophilic adhesion promoter HEMA succinate. In addition, it was confirmed that the adhesive strength of the adhesive film increased as the content of carboxylic acid introduced was increased, and the acrylate reactor bonded at the same ratio as the carboxylic acid maintained the curing density of the adhesive film, so that mechanical properties such as tensile strength and elongation were also excellent. can confirm.

These results provide application to a variety of fields including semiconductors, including low-hygroscopic, high-adhesive adhesive films, which are essential for OLED displays where low moisture absorption characteristics are essential.

In the above, the present invention has been described by specific matters such as specific components and limited embodiments and drawings, but this is provided only to help a more comprehensive understanding of the present invention, and the present invention is not limited to the above embodiments , Those skilled in the art to which the present invention pertains can make various modifications and variations from these descriptions.

Therefore, the spirit of the present invention is not limited to the above-described embodiment, and should not be determined, and all modifications that are equally or equivalent to the claims, as well as the claims to be described later, fall within the scope of the spirit of the present invention. Would say

Claims (13)

(A) at least one selected from maleinized polybutadiene and styrene-maleic anhydride copolymer, and hydroxy ethylene acrylate (Hydroxy Ethylene Acrylate, HEA) and a catalyst is introduced into the reactor and mixed ;
(b) synthesizing the adhesion promoter by raising the temperature inside the reactor to 30-50°C;
(c) mixing the adhesion promoter and the adhesion-imparting agent, the photoinitiator, the plasticizer, the monomer and the oligomer to prepare an ultraviolet curing adhesive resin composition; And
(d) A method of manufacturing a UV curable adhesive resin composition comprising the step of degassing the prepared adhesive resin composition.
According to claim 1,
The method of manufacturing a UV-curable adhesive resin composition, characterized in that the molar ratio of the maleated polybutadiene and hydroxy ethylene acrylate in step (a) is 1: 0.25 to 0.75.
According to claim 1,
The adhesion promoter of step (b) is a reaction of maleinized polybutadiene and hydroxy ethylene acrylate, carboxylate (Acrylates) and hydrophilic carboxylic acid (Carboxyl acid) and maleic acid as main chain polybutadiene. UV curable adhesive resin composition comprising an anhydride (maleic anhydride).
According to claim 1,
The catalyst is dibutyltin dilaurate (Dibutyltin dilaurate) and a method for producing an ultraviolet curable adhesive resin composition, characterized in that it contains 0.1 to 5 parts by weight.
According to claim 1,
In step (c), the adhesion promoter is 5 to 20 parts by weight, the adhesion promoter 0.5 to 15 parts by weight, the photoinitiator 1 to 5 parts by weight, the plasticizer 10 to 50 parts by weight, and the monomer 20 to 100 parts by weight of the adhesive resin composition 50 parts by weight and the oligomer is 30 to 60 parts by weight, UV-curable adhesive resin manufacturing method.
According to claim 1,
The adhesion agent in the step (c) includes at least one member selected from the group consisting of hydroxypropyl acrylate (HPA), hydroxybutyl acrylate (HBA) and hydroxyethyl methacrylate (2-HEMA). Method of manufacturing a UV-curable adhesive resin composition, characterized in that.
According to claim 1,
In the step (c), the photoinitiator is 0.1 to 5 parts by weight of UV curing adhesive resin composition manufacturing method.
According to claim 1,
The method of manufacturing a UV curable adhesive resin composition, characterized in that the plasticizer in the step (c) is 10 to 50 parts by weight.
According to claim 1,
In the step (c), the monomer is a method of manufacturing an ultraviolet curable adhesive resin composition comprising at least one selected from monofunctional to trifunctional acrylate monomers.
According to claim 1, The oligomer in step (c),
(Iii) mixing polybutadiene polyol, isocyanate, diluent, catalyst, and thermal stabilizer and then mixing the mixture while heating the temperature to 40 to 60°C;
(Ii) raising the temperature inside the reactor to 70 to 90° C., and then introducing a curing agent to proceed with the polyurethane reaction;
(Iii) after terminating the exothermic process of the polyurethane reaction, proceeding the reaction for 1 hour to 3 hours to synthesize a prepolymer; And
(I) After the synthesis, a method of manufacturing a UV-curable adhesive resin composition comprising the step of introducing acrylate to the urethane end by adding hydroxyethyl acrylate (HEA) while maintaining 80 to 90°C. .
The method of claim 10,
The polybutadiene polyol is an ultraviolet curing adhesive resin, characterized in that the oligomer is a hydrogenated polybutadiene diol, the diluent is IsoNonyl Acrylate (INA), the catalyst is dibutyltin dilaurate (DBTDL), and a heat stabilizer (BHT). Method of preparing the composition.
The method of claim 10,
The oligomer is a method of manufacturing a UV-curable adhesive resin composition, characterized in that the number average molecular weight is 500 to 10,000.
An ultraviolet curable adhesive resin composition prepared according to any one of claims 1 to 12.

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